Bis-anthraquinoneazoles of azobiphenyldicarboxylic acid



United States Patent Q BIS-ANTHRAQUINONEAZOLFS F AiOBl- PHENYLDICARBOXYLIC ACID Joseph Deinet, Glassboro, N. J., assignor to E.-I.'du Pont de Nemours and Company, Wilmington, Del, a corporation of Delaware No Drawing. Application July 9, 1951, Serial No.. 235,894

6 Claims. (Cl. 260-157) in which X stands for an element of the group consisting of O, S and NH; at least one of the anthraquinone nuclei contains not more than one sulfo group in. one of the positions Y and Z, which sulfo group is of' the formula SO3M' in which M stands for hydrogen or an alkali; metal, more particularly sodium or potassium; and in which one of the remaining positions Y and Z in each of the anthraquinone nuclei stands for an element of the group consisting of -H or halogen, more particularly -Cl and 'Br, and the remaining positions Y' and Z stand for hydrogen.

In the anthraquinone: class of dyes it has been recognized that those in the yellow range are generally deficient in fastness properties, more particularly re gard to, fastness to light. Where yellow dyes have been found in the anthraquinone series which have good 'fastness properties, they are usually dull or weak tinctorially and in general are not adapted for printing by the methods usually employed in the printing of vat dyes, and it has been necessary to select various dyes of the anthraquinone vat dye class, bearing in mind the need for f astness, brightness, tinctorial strength or application properties required for the particular need at hand.

In U. S; Patent 2,175,803 a group of symmetrical dianthraquinone diazoles which contain an azo group in. the molecule are disclosed which dye vegetable fibers in to prepare monoor disulfonic acid derivatives of his anthraquinone oxazoles, thiaroles or imidazoles'of azo biphenyldicarboxylic acids which carry at least one sulfonic acid group in a beta position on at least one of the anthraquinone nuclei.

The azole compounds of this invention are prepared by the general procedures usually employed in the preparation of azole compounds from appropriately substituted aminoanthraquinones and carboxylic acids. In general, the condensation of the substituted animoanthra-- quinone withthe. carboxylic acid is; carried out in a non? reactive organic medium such as nitrobenzene, halogenated benzene, nitrotoluenes, naphthalene, the diandtrichlorobenzenes, and similar organic solvents, preferably in the presence of an organic base such as pyridine, quinoline, dirncthyl aniline, etc.

The bis-oxazolesiare preferably'prepared by condensing a halogenated aminoanthraquinone-beta-sulfonic: acid with) yellow shades which are said to exhibit good fastness to chlorine and boiling soap solution and, in certain cases, to light. It has been found, however, that these dyes are deficient in wet fastness, particularly in kier boiling and vat stability, and are in general not suitable for use as printing colors.

It is an object of the present invention to produce 4,4 '-az obiphenyl-4",4"-dicarboxylic acid in substantially equal moIecular ratio at temperatures of from 120 to 200 C. The resulting mono-condensation product is then further condensed with an aminohalogenanthraquinone or with an aminohalogenanthraquinone sulfonic acid and then ring closed to: the bis-oxazole.

.Thiazoles are preferably prepared by a similar method, starting. with. the mercaptoaminoanthraquinone-beta-sul fonic acid, while the-imida-zoles are prepared by condensing an' ortho-diaminoanthraquinone-beta-sulfonic acid with the azobiphenyldicarboxylic acid chloride.

Mixed types as illustrated by the following examples, such as the oxazol'e thiazoles, oxazole=imidazoles, etc; can be readily prepared by first'condensing an ortho halogenaminoanthraquinone with the azobiphen'yidi carboxylic acid chloride in substantially equal molecular amounts and then condensing the resulting product with a mercaptoaminoanthraquinone or a 1,2-diaminoanthraquinone, at least one of the aminoanthraquinone compounds of course carrying a sulfonic acid group. The resulting compounds are then ring closed to produce the azole rings. In the case of the thiazoles and imidazoles, ring closure to the azole group generally takes place during the: condensation reaction, while the oxazole ring is usually formed by further reaction in the presence of condensation agents such as copper salts and acid binding agents. ,The following examples are given to illustrate the'invention. The parts used are by weight.

Example 1 Twelve hundred (1200) parts of nitrobenzene, 55 parts of 4,4-azobiphenyl-4",4'-dicarboxylic acid sodiurn. salt), 2 parts of pyridine and 43 parts of. thionyl chlo ride are agitated together while heating to from 98 to 100 C., and the reaction mixture is maintained at this temperature for from 15 to 20. hours. After cooling to 50 C. there are added 101 parts of 1-bromo-2-aminoanthraquinonei-3-sulfonic acid (Na) fine' powder. The mass is then heated to from 205 to 208 C. and. maintained' at this temperature for /1 hour. After cooling to C., 50 parts of sodium carbonate, 50 parts of potassium acetate, 1 part of cupric acetate and 1 part of cupi'ous chloride are added. The mass is heated to 210.

. 4 then cooled to 50 C., filtered, the filter cake washed alcohol and water, in turn, and dried. The product is with nitrobenzene, alcohol and water in turn, and dried. then acid pasted and purified by bleaching with sodium The product is then acid pasted by drowning into water hypochlorite. It forms a bright orange-yellow paste and a concentrated sulfuric acid solution of the color, theredyes and prints cotton in bright yellow shades of very after filtering, washing acid free and purifying by bleachgood fastness. ing with sodium hypochlorite. It forms a bright yellow The dye in the form of the sodium salt has the formula:

0 O SC N=N -C-S O l i II SOsNa NaOaS a. I a a paste and dyes and prints cotton or related fibers in strong Example 4 bright yellow shades of excellent fastness properties. Ten hundred 1000 Parts f njtrobenzene, 1 part f This y ill the fOIm 0f the Sodium Salt, hasthe formula? pyridine, 25.7 parts of 1-chloro-2-aminoanthraquinone Example 2 V and 50 parts of 4,4'-azo biphenyl-4",4"-dicarboxylic acid l e hundred (120) Of e e a? R $5225.23 satisfies:ta"; 1. fm? iii. $5.11: of i i 50 parts of azoblp hen-3,14 'ihcarthen cooled to 25 C. and 38 parts of l-mercapto (Na 2 2 g 43 3? fz ag g a salt)-2-aminoanthraquinone-3-sulfonic acid (Na salt) are an eate to rom 0 an main aine a 1 this temperature for 20 hours. After cooling to 50 C., i zg gg g sh ig g gl l g fig i z there are added 30.5 parts of l-chloro-Z-amrnoanthraeramre for 1/ hour The'mas th D co 1 d t quinone. The reaction mass is then heated to from 138 35 and i of sdium g g i to 140 C. and maintained at this temperature for 6 hours. sillm 1 part of cupric acetat andpl 5 5? cu The mass is then cooled to 25 C. and parts of 1- bromo-2-aminoanthraquinone-S-sulfonic acid (K salt) f f g adcied i g i heated to fine powder are added, then heated to from 205 to 208 3 e g s f g z it g ai g gl ig ihi C. and maintained at this temperature for 1.5 hours. The I mass is then cooled to 100 C. and 200 parts of nitroben- 40 E i Washed f alcohol and Water, 111 f and zone, 50 parts of sodlurn carbonate, 50 parts of potassium fie T p f 18 Then acld pasted and P y acetate, 1 part of cupric acetate and 1 part of cuprous bleaching Wlth sodium hypochlorlte- It forms a bllght chloride are added. The mass is then heated at 208 C. yellow paste and dyes and prints cotton or related fibers for 3.5 hours. It is then cooled to 50 C. and the mass in bright yellow shades of very good fastness. filtered, the filter cake washed with alcohol and water, in The dye in the form of the sodium salt has the formula:

NaOaS l) a A turn, and dried. The product is then acid pasted and Example 5 purified by bleaching with sodium hypochlorrte. It forms Ten hundred (1000) Parts of-nitmbenzene, 2 Parts of a bright yellow paste and dyes and prints cotton in strong yellow shades f very good f t pyridine, 55 parts of 4,4-azobiphenyl-4",4"'-d1carboxyl1c The dye in the form of the sodium salt has the formula: acid (sodium salt) and 43 parts of thionyl chloride are (l) OC N=N C(]) E) l H N ii (i 1 Example 3 agitated and heated together at C. for 20 hours.

Eight hundred (800) parts of nitrobenzene, 1 part of Then Parts 1'chloro'z'amznoanthraqumone pyridine, 29 parts of 4,4-azobiphenyl-4",4" -dicarboxylic 79 adds? and the mass 15 heated a for 6 hoursh acid chloride and 47 parts of 1-mercapto-(Na)-2-aminomass 15 then cooled to 40 Parts Of L anthraquinone-Ii-sulfonic acid (Na salt) fine powder are antbfaquiflone-3-slllfonic acid Salt) n Powder are slowly heated together to 210 C. and maintained at this added n then h at t0 208 C. and maintained at this temperature for one-half hour. The mass is then cooled tempefamfii for The s is then cooled to to 25 C., and filtered. The filter cake is washed with 25 C. and 50 parts of sodium carbonate, 50 parts of I v '6 p potassium acetate, 1 part of cupn'c acetate and 1 part of i'ngfito'VO'f C(the reaction mass is filtered and the filter cup'rous; chloride'are added. The reaction mass is: then cake-is washed with alcohol and water'in turn,and""dried. heated at2 'C. for Z'hours; After cooling-to 50 C1, The" p'r'od'uctis then acidpast'ed'andpurified by bleaching the mass is filtered and the filter cake is washed with with sodi'umhypochlorite in the presence of sodium bycarbon tetrachloride. The filter cake is then steam dis- 5 dioxide. It forms a bright yellowpaste and dyes and tilled free from solvents, filtered and the filter cake washed prints cotton in bright yellow shades of "good; fastness alkali'free and'dn'ed. 'Ihefinalproductis-then acid'pasted properties. d r and purified by bleachingwith sodium hypochlorite; It thef'orm of the sodiuin salt hastheforn'iuldi forms. a bright yellow paste and dyes and prints cotton It will be apparent that in preparing the mixed azole in bright yellow shades of very good fastness. compounds the thiazole or imidazole condensation may The product in the form of the sodium salt has the be first effected since this leaves the remaining a cidchloformula: ridetgroup as suchand thcnthe 'l' halogena ahiiiioanthi-a Example 6- a quinone compound maybe condensed and n'iig erases Nine hundred (900) Parts of nitrobenzene, 2 Parts theioxazglchin'place. of Earrying'out thecondensafion of pyridine 43 parts of the specific order given in the above examples. It will boxylic acid and 40 parts of thionyl chloride are heated also be apparent that in making the monoslllfonic acid togethen at 100 C, for 115 h After li to 25," derivatives the condensation may be carried out in either C., 23.8 parts of 1,2-diaminoanthraquinone'are added'and Order desiredthe mass is heated at 170 c. for 1.5 hours. The mass il the products in the above examples have been is then cooled to 2 5 C. and 200 parts of nitrobenzene isolated as the alkali metalsaltsyit will be obvious to and 34' parts of 1,Z-diaminoanthraquinone-3-sulfonic acid those skilled in the art that on acid pasting and drowning (Na salt) fine powder are added. The mass is then 'in water they maybe recovered in the form of the free heated at210 C. for. 3 hours After. cooling to50 C. 40 acidi 1 the mass is filtered, the filter cake washed with alcohol Because of the presence of-the'siilf'onii: acid group' or and water in turn, and dried. The product is then acid groups in the dyes of this invention, these dyes may be pasted and purified by bleaching with; sodium hypochlo prepared for application to the fiber by vatting without rite It forms a bright yellow paste and dyes and prints acid pasting as is often required with aminoanthraquinone cotton in bright yellow shades of good. fastness. The vat dyes particularly with those of similar chemical conproduct in the:form of the sodium salt has the formula: stitution which do not contain the sulfonic acid group.

NC N=N l l -N Example 7 r While anthraquinone vat'dyes. usually do; notcontain Nine hundred (900) parts of nitrobenzene, 2pm. of sulfonic acid groups, it has been found!thatthe dyeseuof pyridine, 43 parts f 4,4' azobiphenyl 4",4"adicarbowlib- I this particular series have improved application propacid and 40 Parts of thionyl chloride are heated togethuerties and vat stability due to the presence of the sulfonic while agitating to 100 C. and. maintained: at. this term acid groups and that they may be applied by the usual perature for 20 hours. The.v mass is then air blown for l printing processes, whereas corresponding dyes not con- 110111 t0 remove BOXCCSS 0f f y chlofidP-v The a 'taining the sulfonic acid groups are not of commercial 33 3;331:1513 g ifig zfigsgfgififiggggfiggigfi value. for application to fibers by the usual printing salt) and 200 Parts of nitrobenzene are' added and the processes reaction mass heated to 120 C. and maintainedrat this I Iheinew compounds of mvemlon are Yellow P temperature-for 6 hours. The mass is then cooled to 25 uctswhich dye and print cotton or related fibers in yellow C. and a milled suspension of 27.7 parts of the sodium shades of excellent strength and fastness properties, parsalt of l-mercapto-2-aminoanthraquinone and: 100. parts fi l lyzfi t it, light of nitrobenzene are added and the mass is -then; slowly Whi] b h heated to 138-140 C. and maintained at this temperaa m the a ova examples t 6 simple ammoanthra mm for 1 hour The mass is then, cooled to 100,, C and, quinone. compounds; containing a sulfonic acid group are 45 parts of sodium carbonate J b of potassium: ace disclosed, there may be; substituted in any of the above tate, 1 part of cupric acetate and 1 part of cuprousi .se em s v correspmlding halogen Substitutfid ride are added. The mass is then.heatedto.205 Q and pounds PIQ Y which contain halogtm in the maintained at this temperature for'2 hours. After cool final molecule. For-instance, in the preparation of the 7 8 .oxazole groups the 1,3-dibromo-2-aminoanthraquinone, in which X stands for an element of the group consisting the l,3-dichloro-2-aminoanthraquinone or the mixed of O, S and NH; at least one of the anthraquinone nuclei chloro-bromo-2-aminoanthraquinone compounds may be contains not more than one sulfo group in one of the poemployed, including those carrying the sulfonic acid in sitions Y and Z, which sulfo group is of the, formula the 6- or 7-positions, or the normallyoccurring mixture 5 SO3Min which M standsfor a member of the group of the 1-halogen-2-aminoanthraquinone?6 (and 7 )-sulconsisting of hydrogen and an alkali metal; and in which fonic acid may be used. In the same manner, in preparone of the remaining positions Y and Z in each of the ing the thiazole group the 1-mercapto-2-amino-3,6 (or anthraquinone nuclei stands for an element of the group 3,7)-halogenanthraquinones may be substituted for the l consisting of H, Cl and Br, and the remaining pomercapto-Z-aminoanthraquinone specifically employed in 10 sitions Y and Z stand for hydrogen. the examples, and in preparing the imidazole groups, 2. The anthraquinone vat dye of the formula:

0 OC N==N C-() O l I I I NaOzS the 1,2-diamino-3-halogenanthraquinone or other halo- 3. The anthraquinone vatdye of the formula: t -gt? i 3 N N -so,m NaOaS &

gen derivative may be used. The halogen compounds 4. The anthraquinone vat dye of the following generdinarily employed will preferably be the chlorine and eral formula:

o-fi- N=N T: s I

Na0 S ll o bromine derivatives, although other halogen derivatives may of Course be Substitutei 5. The anthraquinone vat dye of the formula:

NaOaS I claim:

1. Anthraquinone vat dyes of the general formula:

2 Y Y z ll t 6. The anthraquinone vat dye of the formula: I

SOaNa References Cited in the file of this patent UNITED STATES PATENTS 2,108,126 Honold Feb. 15, 1938 2,175,803 Honold Oct. 1o, 1939 OTHER REFERENCES Georgievics et al., Dye Chemistry, 1920, pages 6 and 7. 

1. ANTHRAQUINONE VAT DYES OF THE GENERAL FORMULA: 